EP1209204A1 - Anthrapyridonverbindung, waessrige magenta tintenzusammensetzungen sowie tintenstrahlaufzeichnungsverfahren - Google Patents

Anthrapyridonverbindung, waessrige magenta tintenzusammensetzungen sowie tintenstrahlaufzeichnungsverfahren Download PDF

Info

Publication number
EP1209204A1
EP1209204A1 EP00955064A EP00955064A EP1209204A1 EP 1209204 A1 EP1209204 A1 EP 1209204A1 EP 00955064 A EP00955064 A EP 00955064A EP 00955064 A EP00955064 A EP 00955064A EP 1209204 A1 EP1209204 A1 EP 1209204A1
Authority
EP
European Patent Office
Prior art keywords
ink
water
formula
salt
compound represented
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP00955064A
Other languages
English (en)
French (fr)
Other versions
EP1209204A4 (de
EP1209204B1 (de
Inventor
Hiroyuki Matsumoto
Yasuo Murakami
Junko Yoshioka
Yasuo Shirasaki
Katsunori Fujii
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Kayaku Co Ltd
Original Assignee
Nippon Kayaku Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Kayaku Co Ltd filed Critical Nippon Kayaku Co Ltd
Publication of EP1209204A1 publication Critical patent/EP1209204A1/de
Publication of EP1209204A4 publication Critical patent/EP1209204A4/de
Application granted granted Critical
Publication of EP1209204B1 publication Critical patent/EP1209204B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0023—Digital printing methods characterised by the inks used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0041—Digital printing on surfaces other than ordinary paper
    • B41M5/0064—Digital printing on surfaces other than ordinary paper on plastics, horn, rubber, or other organic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B5/00—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings
    • C09B5/02—Dyes with an anthracene nucleus condensed with one or more heterocyclic rings with or without carbocyclic rings the heterocyclic ring being only condensed in peri position
    • C09B5/14—Benz-azabenzanthrones (anthrapyridones)
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/009—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using thermal means, e.g. infrared radiation, heat

Definitions

  • the present invention relates to an ink composition, more particularly, to a water-soluble magenta ink composition for ink-jet recording comprising a anthrapyridone compound or the salt thereof that has a wide color range and is excellent in color tone, light fastness and water fastness; and a method of ink-jet recording thereby.
  • the information is generally printed by subtractive color mixing of inks of four colors, namely yellow(Y), magenta(M), cyan(C) and black(K).
  • the dyes used therefor are desired to have color hues close to the respective standards of YMC ("Japan Color Standard Paper” published by Japan Printing Machinery Manufacturers Association)and vividness.
  • the resulting ink composition is stable for long-term storage and that the resulting printed image is of a high optical density and has excellent fastness including water fastness, light fastness, and outdoor exposure fastness.
  • Outdoor exposure fastness is a complex fastness to light and atmospheric gas such as the oxide gas of nitrogen or sulfur and ozone.
  • the present invention relates to a magenta ink.
  • ink-jet printers are enlarged from a small one for office use to a big one for industry. So, excellence in fastness such as water fastness and light fastness of the printed image is more keenly demanded.
  • the water fastness of an article recorded by ink-jet printing has been improved substantially by coating inorganic or organic micro particles such as cationic polymer, porous silica, alumina sol and special ceramics which can absorb dye from ink, on a paper sheet together with the resins such as PVA resin.
  • Various coated sheets for ink-jet printing are already available on the market. But light fastness has not yet been largely improved by any established technique.
  • magenta one of tetrachromatic colors of YMCK, of which dyes are originally poor in light fastness, and the improvement is an important problem to be solved. Further, the articles recorded by magenta dyes have been found to fade in color while being exposed to light and air, possibly because of the influences of the various gasses existing in nature.
  • the chemical structure of magenta dyes used in a water-soluble ink for ink-jet recording are a xanthene type disclosed by JP Laid-Open No.89811/1979, JP Laid-Open No.60053/1996 and JP Laid-Open No.143798/1996, and an azo type using the H acid disclosed by JP Laid-Open No.62562/1986, JP Laid-Open No.156168/1987, JP Laid-Open No.203970/1991, JP Laid-Open No.157698/1995 and JP Publication No.78190/1995.
  • the xanthene type is indeed excellent in hue and vividness, but is very inferior in light fastness.
  • Some of the azo type using the H acid are good in hue and water fastness, but are inferior in light fastness and vividness.
  • magenta dyes having excellent vividness and light fastness have been developed in this type, but are still inferior in light fastness to the dyes of other colors such as azo yellow dyes and cyan dyes represented by copper phthalocyanine type.
  • an anthrapyridone type is known as disclosed by JP Laid-Open No.195775/1982, JP Laid-Open No.74173/1984 and JP Laid-Open No.16171/1990 but is not yet able to satisfy all of the properties such as the range of color, hue, vividness, light fastness, water fastness and stability in solution.
  • An anthrapyridone compound is described as a dye having good light fastness and water fastness in USP No.2,644,821. However, it is a dye mainly for fiber dyeing and can not provide a high quality ink suitable for ink-jet recording.
  • An object of the present invention is to provide a water-based magenta ink composition which has hue of a wide color range and vividness suitable for ink-jet recording and gives the recorded material with a high fastness and a magenta dye suitable therefor.
  • the present invention is as follows:
  • the axis X represents a* value and the axis Y represents b* value on the L* a* b* colorimetric system.
  • Y shows yellow
  • R shows red
  • M shows magenta
  • B shows blue
  • C shows cyan
  • G shows green.
  • the solid line expresses the color range of the ink composition of Example 4 and the dotted line expresses the color range of the ink composition of Comparative Example 1.
  • the axis X represents a* value
  • the axis Y represents b* value on the L* a* b* colorimetric system.
  • Y shows yellow
  • R shows red
  • M shows magenta
  • B shows blue
  • C shows cyan
  • G shows green.
  • the solid line expresses the color of the printed product in Example 6 and the dotted lines express the color ranges of the printed products in Comparative Example 3, 4 and 5.
  • the anthrapyridone disulfonic acid represented by above Formula (1) of the present invention or the salt thereof can be obtained for example by sulfonating the compound represented by above Formula (2) in sulfuric acid containing fuming sulfuric acid.
  • the concentration of fuming sulfuric acid in sulfuric acid is 5-12% by mass, preferably 6-10% by mass.
  • the reaction temperature is generally 0- 60°C preferably 10-30°C.
  • the reaction time though it varies depending on the reaction temperature, is generally 5 minutes-20 hours, 30 minutes-5 hours under the preferable condition.
  • the progress of the sulfonation reaction can be traced by high performance liquid chromatography (HPLC).
  • the disufonic acid product of the compound represented by above Formula (2) is not always needed to be pure to use for preparing the ink composition of the present invention.
  • the dye mixture which is obtained by sulfonating the compound represented by above Formula (2) and contains the disulfonic acid product of the compound represented by above Formula (2) as the principal component, can be used even if it contains the monosulfonic acid product of the compound represented by above Formula (2).
  • Such a dye mixture can be produced, for example, by sulfonating the compound represented by above Formula (2) in sulfuric acid containing fuming sulfuric acid.
  • the concentration of fuming sulfuric acid in sulfuric acid is 5-12% by mass, preferably 6-10% by mass.
  • the reaction temperature is generally 0-60°C preferably 10-30°C.
  • the reaction time is generally 5 minutes-20 hours.
  • the degree of sulfonation is examined in terms of area ratio by high performance liquid chromatography (HPLC).
  • HPLC high performance liquid chromatography
  • the reaction is terminated when the compound represented by above Formula (2) disappears and the monosulfonic acid product decreases to a concentration of about 10% by mass or less.
  • the reaction solution is poured into ice water, salted out, filtered, and dried to get a dye mixture containing the targeted disulfonic acid product or the salt thereof as the principal component.
  • the disulfonic acid product or the salt thereof thus obtained comprises mainly the anthrapyridone disulfonic acid represented by above Formula (1) or the salt thereof.
  • the other components contained in the obtained dye mixture include the monosulfonic acid product of the compound represented by above Formula (2) or the salt thereof and inorganic salts.
  • the content of the monosulfonic acid product is preferably as low as possible for the facility of production (such as filterability) of an ink, the storage stability of an ink, and the vividness of a recorded product and is 10% or less(including 0%), preferably 5% or less, more preferably 2% or less, most preferably 1% or less, when determined from area ratios by high performance liquid chromatography for example.
  • the content of the dinosulfonic acid product of the compound represented above by Formula (2) or the salt thereof is 85% or more, preferably 90% or more, more preferably 92% or more, most preferably 95% or more, when determined from area ratios by high performance liquid chromatography.
  • the compound represented by above Formula (1) of the present invention is preferable because it is easy to be manufactured and suitable for an ink composition and so on.
  • HPLC high performance liquid chromatography
  • a compound or a dye mixture of the present invention to use has preferably an inorganic salt content as low as possible for preparing an ink composition of the present invention.
  • the aiming total content of sodium chloride and sodium sulfate, for example, in the compound or the dye mixture of the present invention is 1% by mass or less, preferably 0.5% by mass or less.
  • the content of inorganic salts can be determined respectively as follows: Cl - and SO 4 2 - by ion chromatography; a heavy metal ion by atomic absorption spectrometry or ICP(Inductively Coupled Plasma)emission spectrometry; Ca 2 + and Mg 2 + by ion chromatography, atomic absorption spectrometry or ICP emission spectrometry.
  • the compound or the dye composition of the present invention is preferably treated with a lower alcohol such as methanol and ethanol if necessary so that it may have an inorganic salt content as low as possible for preparing an ink composition of the present invention.
  • the other desalting treatment includes a conventional method using reverse osmotic membrane and a method that a dry product or a wet cake, preferably a wet cake, of the dye component of the present invention (the compound or the dye composition of the present invention) is stirred in a solvent such as hydrous lower alcohol, preferably in a mixture solvent of methanol with water, then filtered and dried. Any of them is applicable, however, the latter method is more preferable.
  • the solvent amount (mass) is about 1-20 times, preferably about 2-10 times as much as the dry product or the wet cake.
  • the treating time though not particularly limited because it varies depending on the amount to treat, the amount of hydrous lower alcohol and any other conditions, is generally several minutes to several hours, preferably about 10 minutes-3 hours.
  • the treating temperature though not particularly limited, is generally about 10-40°C, preferably about room temperature.
  • the alcohol content in the hydrous lower alcohol is generally about 20-95% by mass, preferably 50-90% by mass, more preferably 70-85% by mass.
  • the compound or the dye mixture of the present invention can exist as a free acid or the salt thereof.
  • the salt can be used as the alkali metal salt, an alkali earth metal salt, an alkylamine salt, an alkanolamine salt or an ammonium salt.
  • the preferable salts are an ammonium salt; an alkali metal salt such as the sodium salt, the potassium salt and the lithium salt; and an alkanolamine salt such as the monoethanolamine salt, the diethanolamine salt, the triethanolamine salt, the monoisopropanolamine salt, the diisopropanolamine salt and the triisopropanolamine salt.
  • the sodium salt for example can be obtained by adding the sulfonation reaction solution into ice water after sulfonating , then salting out with sodium chloride and filtering.
  • the sodium salt is dissolved in water, followed by acidifying the solution with an acid to deposit a crystal, and then filtered to obtain a wet cake of dye as the free acid.
  • the dye in the form of the free acid is dissolved or suspended in water, followed by adding and dissolving a base corresponding to the objective salt such as an amine or a compound of other alkali metal than sodium to get a solution of each salt.
  • Other salts than the sodium salt can be obtained conventionally by depositing from the solution, filtering and drying.
  • the water-based ink composition of the present invention can be obtained by dissolving the above dye component in water or an aqueous solvent(water containing a water-soluble organic solvent which will be described later).
  • the preferable ink pH is about 6 to 11.
  • a dye component containing an inorganic salt such as the chloride and the sulfate of a metal positive ion, as little as possible when using for an ink-jet recording printer.
  • the water-based ink composition of the present invention is prepared by using water as a medium, containing the dye component preferably by 0.1 to 20% by mass, more preferably by 1 to 10% by mass, further more preferably 2 to 8% by mass.
  • the water-based ink composition of the present invention also may contain a water-soluble organic solvent in about 60% by mass or less, preferably in about 50% by mass or less, more preferably in about 40% by mass or less, further more preferably in about 30% by mass or less.
  • the minimum amount may be 0%, however, it generally contain in about 5% by mass or more, preferably in about 10% by mass or more and most preferably in 10-30% by mass.
  • the water-based ink composition of the present invention also may contain the additives for preparation of ink in about 0 to 10% by mass, preferably by 5% by mass or less. The remainder is water.
  • the usable water-soluble organic solvent includes a C1 - C4 alkanol such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol and tertiary butanol; a lower carboxylic (mono or di)lower alkylamide such as N,N-dimethylformamide and N,N-dimethylacetoamide; a lactam, preferably a 4 membered ring to 8 membered ring of lactam such as ⁇ -caprolactam and N-methylpyrrolidin-2-one; urea; a cyclic urea, preferably a 5-6 membered ring of cyclic urea such as 1,3-dimetylimidazolidin-2-one or 1,3-dimethyl hexahydropyrimid-2-one; a C4-C7 straight chain of ketone or keto-alcohol such as acetone,
  • the preferable solvents include water and N-methylpyrrolidin-2-one, a mono-, di- or tri-alkylene glycol having C2 - C6 alkylene units ( preferably mono-, di- or triethylene glycol, dipropylene glycol), and dimethylsulfoxide.
  • the use of N-methylpyrrolidin-2-one, diethylene glycol, and dimethylsulfoxide are especially preferable.
  • the additives for preparation of the ink include all of the components excluding the water, the dye component and the water-soluble organic solvent described above. It includes such as a preservative, a pH- adjusting agent, a chelating reagent, a rust preventive, a water-soluble ultraviolet absorbing agent, a water-soluble polymer compound, and a surfactant.
  • the preservative includes sodium dehydroacetate, sodium sorbate, sodium 2-pyridine thiol-1-oxide, sodium benzoate and sodium pentachlorophenolate.
  • the pH-adjusting agent includes any substance that can control the ink pH within a range of 6 to 11 as long as it has no adverse effect on the ink preparation.
  • the examples are alkanolamines such as diethanolamine and triethanolamine; alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; ammonium hydroxide; or alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate.
  • the chelating reagent includes sodium ethylenediamine tetraacetate, sodium nitrilotriacetate, sodium hydroxylethylenediamine triacetate, sodium diethylenetriamine pentaacetate, and sodium uramil diacetate.
  • the rust preventive includes acidic hyposulfite salts, sodium thiosulfate, ammonium thioglycolate, diisopropylammoniumnitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.
  • the ink composition of the present invention is prepared by adding the dye of the present invention into the impurity-free water such as distilled water and then mixing together with the above water-soluble organic solvent and the additives for preparation of the ink upon necessity.
  • the dye of the present invention may be added in a mixture of water, the above water-soluble organic solvent and the additives for preparation of the ink to dissolve.
  • the resulting ink composition may be filtered, if necessary, to remove the contaminants from the composition.
  • the aiming total content of sodium chloride and sodium sulfate, for example, as an inorganic salt in the ink composition of the present invention is preferably 0.1% by mass or less, and more preferably 0.05% by mass or.
  • a recording material used in ink-jet recording of the present invention includes an information transmission sheet such as paper and film, fiber and leather.
  • the information transmission sheet is surface-treated and, practically, is the one having an ink-acceptable layer on the basement material.
  • the ink-acceptable layer can be made, for example, by impregnating or coating a cationic polymer on the above basement material; or by coating an inorganic fine-grain such as porous silica, alumina sol and special ceramic, which can absorb the dye from an ink, together with a hydrophilic polymer such as polyvinyl alcohol and polyvinyl pyrrolidone on the above basement material.
  • the sheet having the ink-acceptable layer is generally called a special ink-jet paper (film) or a glossy paper (film), and is available on the market, for example, as Pictorico(by Asahi Glass KK), Color BJ Paper, Color BJ Photofilm sheet(by Canon KK), Color Image Jet special paper(by Sharp KK), Superfine special glossy film(by Seiko Epson KK)and Pictafine(by Hitachi Maxell KK).
  • a plain paper can of course be used for a recording material.
  • the preferable fiber is a polyamide fiber such as nylon, silk and wool in the form of nonwoven fabric or cloth.
  • the ink composition of the present invention is applied to the fiber, preferably by ink-jetting, followed by fixing by wet heating (for example, about 80-120°C) or dry heating(for example, about 150-180°C). so that the dye can be fixed inside the fiber to give a colord article having excellent grade in vividness, light fastness and washing fastness.
  • a container containing the above water-based magenta ink composition is set in an ink-jet printer to record on the above recording material by a conventional method.
  • the ink-jet printer includes a piezo system printer using a mechanical vibration and a bubble-jet system printer using bubble generated by heating.
  • the above water-based magenta ink composition can be used in combination with a yellow ink composition, a cyan ink composition, or a black ink composition if necessary.
  • a water-based cyan ink composition as a cyan ink composition containing water-soluble metal phthalocyanine dye, if used in combination with the above water-based magenta ink composition shows less change in the color tone in the light fastness test executed after color blending.
  • the metal in the water-soluble metal phthalocyanine dye includes copper, nickel and aluminium.
  • the copper is preferable.
  • the water-soluble copper phthalocyanine dye includes C.I Direct Blue 86, C.I.Direct Blue 87, C.I.Direct Blue 199, C.I.Acid Blue 249, C.I.Reactive Blue 7, C.I.Reactive Blue 15, C.I.Reactive Blue 21, and C.I.Reactive Blue 71.
  • the cyan ink composition containing the water-soluble metal phthalocyanine dye can be produced, for example, according to the method for producing the above water-based magenta ink composition, and then injected into a container.
  • the container is set to use at the indicated position of an ink-jet printer in the same way as the container containing the water-based magenta ink composition.
  • the water-based ink composition of the present invention can give an ideal magenta color that has vividness, a color tone close to the one shown in the above Japan Color, high chroma and an appropriate bluishness. Therefore, the composition, if used together with a yellow or cyan ink, can give a wide range of color in visible color tone. Further, the composition, if used together with an existing yellow, cyan or black ink which is excellent in light fastness and water fastness, can provide a recorded product with excellent grade in light fastness and water fastness.
  • the solution thus obtained was filtered and washed with 20 parts of 10% aqueous sodium chloride solution to get a wet cake, which was then stirred with 300 parts of water for 30 minutes and filtered to remove a small amount of undissolved product.
  • 30 parts of sodium chloride was added under stirring in the mother liquor to salt out, followed by stirring for 1 hour, filtering, and drying to obtain a dye mixture containing the disulfonic acid product of the anthrapyridone compound of Formula (2) as the main component (containing the monosulfonic acid product of the compound of Formula (2)) (a dye component to use in the present invention) as a reddish powder.
  • the dye mixture was analyzed by high performance liquid chromatography (HPLC) to determine an area ratio.
  • HPLC high performance liquid chromatography
  • the sodium salt was analyzed by high performance liquid chromatography (HPLC) to determine an area ratio.
  • HPLC high performance liquid chromatography
  • the area ratio by the HLPC revealed that the sodium salt thus obtained contained the sodium anthrapyridone disulfnate represented by Formula (1) in the content of 95% or more and the sodium monosulfonate of the anthrapyridone compound represented by Formula (2) in that of 10% or less.
  • the content of NaCl is 0.1% and that of Na 2 SO 4 is 0.2%.
  • the sodium salt thus obtained contained the sodium monosulfonate of the anthrapyridone compound represented by Formula (2) in the content of 0.2% and the sodium anthrapyridone disulfnate represented by Formula (1) in that of 95.0%.
  • the liquid having a constitution as described below in Table 1 was prepared and then filtered through a 0.45 ⁇ m membrane filter to obtain a water-based ink composition for ink-jetting.
  • the ink composition deposited no crystal after a 6 month storage, and so was good in storage stability.
  • Dye of the present invention (The compound of Example 1:M1)(note) 4.5 parts Water 75.5 parts N-methylpyrrolidine-2-one 5.0 parts Etylene Glycol 5.0 parts Glycerin 5.0 parts Urea 5.0 parts Total 100.0 parts (note)The content of the monosulfonic acid product: 0.5% or less (as determined by HPLC at the above condition); The total content of sodium chloride and sodium sulfate: 1% by mass or less; The solubility in pure water(ion exchanged water): 100g/L (25°C)
  • ink-jet printer (Trade name: BJ F600, made by Canon KK)
  • ink-jet recordings were done with a monochrome and a blend color (red, blue, green) on a commercially available plain paper(PB PAPER, made by Canon KK) and a glossy film (a photo glossy film, HG-201, made by Canon KK) having a dye-acceptable layer.
  • PB PAPER plain paper
  • HG-201 a photo glossy film
  • a recorded paper was subject to color determination using the colorimeter (GRETAG SPM50, made by GRETAG Co.) to calculate L* ,a* ,b* values.
  • a carbon arc fade meter (made by Suga Testing Machine Co.) was used to irradiate carbon arc on the recorded papers for 40 hours. A change in grade between before and after the irradiation was judged according to JIS blue scale. A color difference( ⁇ E)between before and after the irradiation also was measured by the above color determination system. The results are shown in Table 2. Hue Vividness Light fastness L* a* b* C* Grade( ⁇ E) JNC standard magenta 46.3 74.4 -4.4 74.5 Magenta ink of Ex.3 46.6 78.9 -14.6 80.2 5(14.5)
  • Example 3 in the present invention reveals that the ink composition of Example 3 in the present invention is excellent because it is similar to the standard magenta in hue and vividness and shows a small color difference between before and after the irradiation in light fastness test on a coated paper.
  • the dye component to use in the present invention is an excellent dye for ink-jetting because it has a water-solubility of about 100g/L, and can prepare a high concentration of ink.
  • the dye (M1) of the present invention was used to prepare a magenta ink in the same way as done in Example 3.
  • the dye (M2:C.I.Acid Red 82)as described in JP Laid-Open No.195775/1982 was used to prepare a magenta ink for an comparative example, wherein this ink was adjusted to coincide with the above ink in optical density.
  • the inks attached to the printer (Trade name: BJ F600, made by Canon KK) were used for an yellow ink and a cyan ink.
  • the cyan ink comprised a water-soluble phthalocyanine dye.
  • ink-jet printings were done with a monochrome and a blend color (red, blue) on a commercially available glossy film(a photo glossy film, HG-201, made by Canon KK). The printings also were done with yellow, cyan and their blend color for reference.
  • Table 3 reveals that the magenta color of Comparative Example 1 was yellowish and different from the standard magenta color because its b* value was positive and that the magenta color to use in the present invention was a nearly ideal magenta color with appropriately bluish tone because its b* value was -14.6. Further its blend color with the cyan was blue having the b* value of a of -62.8, which is more strongly bluish.
  • the a* values and the b* values in Table 3 are plotted on a chromaticity diagram as illustrated in Fig.
  • magenta of the present invention has a larger extent in the region of positive a* values and negative b* values than the magenta of Comparative Example 1 and so can give a greater number of blend colors having color tone involved in this region. Further, the magenta of the present invention is found out to have higher vividness from its C* value as a criterion of vividness. The above results shows that the ink composition of Example 4 has a higher vividness and an enlarged range of colors, and has especially superiority in B(blue) and M(magenta).
  • magenta color to use in the present invention is superior to Comparative Example 1 because the color change in outdoor exposure fastness test is smaller than that of Comparative Example 1 and especially, have considerably superiority in magenta color and blend blue color.
  • magenta color to use in the present invention and its blended colors of red and blue were better in water fastness.
  • a magenta ink composition was prepared in the same way as in the ink composition of Example 3 except that 3.8 parts of the dye (M1) containing the compound of Formula (1) and 76.2 parts of water were used instead.
  • the ink (M3) confirmeded to be an azo dye for the below printer was used for Comparative Example 2.
  • the cyan ink composition also was prepared in the same way as in Example 3 except that the below copper phthalocyanine dyes were used instead.
  • ink-jet printer (Trade name: BJ F600, made by Canon KK)
  • ink-jet printings were done with a monochrome and a blend color (blue) on a commercially available plain paper (Trade name: PB PAPER, made by Canon KK) and a glossy film(a photo glossy film, HG-201, made by Canon KK).
  • a carbon arc fade meter (made by Suga Testing Machine Co.) was used to irradiate carbon arc on the recorded papers for 40 hours.
  • a color difference( ⁇ E)between before and after the irradiation was measured by the colorimeter (SPM50, made by GRETAG Co.). The results are shown in Table 4. No.
  • No.1-1 to 1-3 are the test samples made from the ink compositions of the present invention, and No.2-1 to 2-3 are the comparative samples. All the data in No. 1-1 to 1-3 are superior to those in No.2-1 to 2-3. In comparison between No. 1-1 and No.2-1, No. 1-1 does not give a big difference in color difference between a plain paper and a glossy film, whereas No .2-1 brings a larger difference in color difference on a glossy film than in that on a plain paper.
  • both No.1-2 and No.1-3 of Example 5 stand between the magenta only and their respective cyan only in ⁇ E value, while both No.2-2 and No.2-3 are beyond any of the magenta only and their respective cyan only in ⁇ E value on the glossy film.
  • This fact means that a combination with the copper phthalocyanine cyan dye, which may bring a large decrease of light fastness depending on a recording paper (film) in case of the dye of Comparative Example 2, can inhibit a decrease of light fastness in the case of the dye of the present invention.
  • the combinations in Example 5 have their respective small deviations in ⁇ E value among them, whereas those in Comparative Example 2 have their large deviations. Therefore, the combinations in Comparative Example 2 bring large difference on the printed images, whereas those in Example 5 of the present invention can lighten gradually and uniformly the whole printed images without large difference brought about on the printed image. There is especially shown a significant difference on a glossy film suitable for printing an image.
  • the dye (M1) of the present invention was used to prepare a magenta ink for an example in the same way as done in Example 3.
  • the dye (M2:C.I.Acid Red 82)as described in JP Laid-Open No.195775/1982 was used to prepare a magenta ink for Comparative Example 3;
  • the dye (M4) as described in Jp Laid-Open No.74173/1984 and represented by below Formula (3) was used to prepare a magenta ink for Comparative Example 4;
  • the dye (M5) as described in JP Laid-Open No.74173/1984 and represented by below Formula (4) for Comparative Example 5 was used to prepare respective magenta ink for Comparative Examples, wherein these magenta inks were adjusted to coincide with the above ink composition in optical density.
  • the inks attached to the printer (Trade name: BJ F850, made by Canon KK) were used for an yellow ink and a cyan ink.
  • the cyan ink comprised a water-soluble phthalocyanine dye.
  • ink-jet printings were done with a monochrome and a blend color (red, blue) on a commercially available glossy film (a photo glossy film, HG-201, made by Canon KK) .
  • the printings also were done with yellow, cyan and their blend color for reference.
  • Table 5 reveals that the magenta colors of Comparative Example 3, 4 and 5 were yellowish and different from the standard magenta color because their b* values are positive, that the magenta color of the present invention was a nearly ideal magenta color which is appropriately bluish because its b* value was -12.4, and further that its blended color with the cyan is blue color having b* value of -62.4, namely stronger blue.
  • the a* values and the b* values in Table 5 are plotted on a chromaticity diagram as illustrated in Fig.2 to reveal that the magenta of the present invention has a larger extent in the region of positive a* values and negative b* values than the magentas of Comparative Example 3, 4 and 5 and so can give a greater number of blend colors having hue involved in this region. Further, the magenta of the present invention is found out to have a higher C* value as a criterion of vividness. The above results shows that the ink composition of Example 6 has a higher vividness and a wider range of color rendering, and has especially superiority in R(red), B(blue) and M(magenta).
  • the anthrapyridone compound of the present invention is excellent in water-solubility, and characterized by having a good ability to filter through a membrane filter in the production process of an ink composition.
  • the compound is highly safe for a living body.
  • the ink composition of the present invention using the anthrapyridone compound does not show a crystal deposition after a long storage, a change in property(an aging change in viscosity, surface tension and so on) and a color change, so that it has good storage stability.
  • the ink composition of the present invention when used as a magenta ink for ink-jet recording, can provide a printed matter with excellent grade in light fastness, outdoor exposure fastness and water fastness.
  • the composition when used together with a yellow, cyan or black dye, can give an ink-jet recorded matter that is excellent in light fastness, outdoor exposure fastness and water fastness.
  • the composition when used to apply to an information recording paper and especially to an information paper having an ink-acceptable layer, can bring a remarkable effect.
  • the composition also can provide a vivid printed surface as well as an ideal magenta color.
  • the composition when used together with a yellow or cyan ink, can provide a wide visible ray range of color tone.
  • the compound of the present invention is very useful for an ink-jet recording magenta ink.
EP00955064A 1999-09-03 2000-08-28 Anthrapyridonverbindung, waessrige magenta tintenzusammensetzungen sowie tintenstrahlaufzeichnungsverfahren Expired - Lifetime EP1209204B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP25085599 1999-09-03
JP25085599 1999-09-03
PCT/JP2000/005792 WO2001018123A1 (fr) 1999-09-03 2000-08-28 Compose d'anthrapyridone, compositions aqueuses d'encre magenta et procede d'impression a jet d'encre

Publications (3)

Publication Number Publication Date
EP1209204A1 true EP1209204A1 (de) 2002-05-29
EP1209204A4 EP1209204A4 (de) 2002-11-05
EP1209204B1 EP1209204B1 (de) 2004-03-03

Family

ID=17214017

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00955064A Expired - Lifetime EP1209204B1 (de) 1999-09-03 2000-08-28 Anthrapyridonverbindung, waessrige magenta tintenzusammensetzungen sowie tintenstrahlaufzeichnungsverfahren

Country Status (8)

Country Link
US (1) US6648952B1 (de)
EP (1) EP1209204B1 (de)
KR (1) KR100674095B1 (de)
CN (1) CN1314766C (de)
CA (1) CA2383143A1 (de)
DE (1) DE60008760T2 (de)
TW (1) TW538098B (de)
WO (1) WO2001018123A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1375612A1 (de) * 2002-06-26 2004-01-02 Konica Corporation Tintenstrahltinte, Tintenstrahlaufzeichnungsverfahren und damit aufgezeichnetes bilderzeugendes Material

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6481841B1 (en) 2001-08-01 2002-11-19 Eastman Kodak Company Ink jet printing method
US6685768B2 (en) 2001-08-01 2004-02-03 Eastman Kodak Company Ink jet ink set
US6511170B1 (en) 2001-08-01 2003-01-28 Eastman Kodak Company Ink jet printing method
US6706102B2 (en) 2001-08-01 2004-03-16 Eastman Kodak Company Dye mixture for ink jet ink
US6511169B1 (en) 2001-08-01 2003-01-28 Eastman Kodak Company Ink jet printing method
US6669768B2 (en) 2002-03-08 2003-12-30 Eastman Kodak Company Ink jet ink set
US6669767B2 (en) 2002-03-08 2003-12-30 Eastman Kodak Company Ink jet printing process
US20040139883A1 (en) * 2003-01-16 2004-07-22 Harish Goswamy Novel water based liquid ink and method of manufacturing the water based (aqueous) liquid inks for use in different types of ink jet printers
US20050003301A1 (en) * 2003-01-29 2005-01-06 Orient Chemical Industries, Ltd. Laser ray transmitting colored thermoplastic resin composition and method of laser welding
KR101174741B1 (ko) * 2005-01-17 2012-08-17 니폰 가야꾸 가부시끼가이샤 안트라피리돈 화합물, 마젠타 잉크 조성물 및 착색체
US7533980B2 (en) 2005-02-15 2009-05-19 Hewlett-Packard Development Company, L.P. Ink set and media for ink-jet printing
US20100221502A1 (en) * 2005-08-09 2010-09-02 Hiroyuki Matsumoto Anthrapyridone Compound and Salt Thereof, Magenta Ink Composition Containing the Anthrapyridone Compound, and Colored Article
KR101493918B1 (ko) * 2007-11-06 2015-02-16 니폰 가야꾸 가부시끼가이샤 안트라피리돈 화합물 또는 그의 염, 마젠타 잉크 조성물 및 착색체
US20120056931A1 (en) * 2009-05-18 2012-03-08 Nippon Kayaku Kabushiki Kaisha Magenta coloring matter, ink composition, and colored body
US8277550B2 (en) * 2009-07-15 2012-10-02 Lexmark International, Inc. Yellow inkjet ink having improved print quality with porous photo media
US8282723B2 (en) * 2009-07-15 2012-10-09 Lexmark International, Inc. Magenta inkjet ink having improved print quality with porous photo media
US8256885B2 (en) * 2009-07-15 2012-09-04 Lexmark International, Inc. Cyan inkjet ink having improved print quality with porous photo media
US8328920B2 (en) * 2009-07-15 2012-12-11 Lexmark International, Inc. Inkjet ink having improved high resolution nozzle plate compatibility
JPWO2012070645A1 (ja) * 2010-11-26 2014-05-19 日本化薬株式会社 インクジェット記録用インクセット、記録方法及びそれを用いた着色体
WO2012094820A1 (zh) 2011-01-14 2012-07-19 大连理工大学 蒽吡啶酮磺酸化合物及其制备方法和用途
CN102741354B (zh) 2011-09-01 2013-11-20 大连理工大学 羰丙砜基蒽吡啶酮磺酸化合物及其制备方法和用途
TWI615447B (zh) 2013-08-08 2018-02-21 Nippon Kayaku Kk 墨水組成物、使用此墨水組成物之噴墨記錄方法、及著色體

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2644821A (en) * 1953-07-07 Anthrapyridone dyestuffs
EP0270306A2 (de) * 1986-12-01 1988-06-08 Sumitomo Chemical Company, Limited Anthrapyridon-Verbindungen, ihre Herstellung und ihre Verwendung
JPH0216171A (ja) * 1988-07-05 1990-01-19 Ricoh Co Ltd 水性インク
JPH0829771A (ja) * 1994-07-15 1996-02-02 Canon Inc カラーフィルタ、その製造方法、及びカラーフィルタを備えた液晶パネル
EP0927747A1 (de) * 1996-09-11 1999-07-07 Nippon Kayaku Kabushiki Kaisha Anthrapyridonverbindungen, wässrige tintenzusammensetzung und die damit gefärbten gegenstände
WO1999046341A1 (fr) * 1998-03-10 1999-09-16 Nippon Kayaku Kabushiki Kaisha Composition d'encre magenta a base aqueuse et procede d'impression par jet d'encre

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5974173A (ja) 1982-10-22 1984-04-26 Nippon Kayaku Co Ltd 赤色水性インク
JPH03100502A (ja) * 1989-09-13 1991-04-25 Nippon Kayaku Co Ltd カラーフィルター
JPH0597417A (ja) * 1991-10-03 1993-04-20 Idemitsu Kosan Co Ltd フラーレン類の精製方法
JP3100502B2 (ja) 1994-02-28 2000-10-16 三洋電機株式会社 自動洗髪機
DE69938238T2 (de) * 1998-03-25 2008-06-12 Nippon Kayaku K.K. Anthrapyridonverbindungen, magentatintenzusammensetzungen auf wasserbasis sowie verfahren zur tintenstrahlaufzeichnung
US6481841B1 (en) * 2001-08-01 2002-11-19 Eastman Kodak Company Ink jet printing method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2644821A (en) * 1953-07-07 Anthrapyridone dyestuffs
EP0270306A2 (de) * 1986-12-01 1988-06-08 Sumitomo Chemical Company, Limited Anthrapyridon-Verbindungen, ihre Herstellung und ihre Verwendung
JPH0216171A (ja) * 1988-07-05 1990-01-19 Ricoh Co Ltd 水性インク
JPH0829771A (ja) * 1994-07-15 1996-02-02 Canon Inc カラーフィルタ、その製造方法、及びカラーフィルタを備えた液晶パネル
EP0927747A1 (de) * 1996-09-11 1999-07-07 Nippon Kayaku Kabushiki Kaisha Anthrapyridonverbindungen, wässrige tintenzusammensetzung und die damit gefärbten gegenstände
WO1999046341A1 (fr) * 1998-03-10 1999-09-16 Nippon Kayaku Kabushiki Kaisha Composition d'encre magenta a base aqueuse et procede d'impression par jet d'encre

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN & JP 02 016171 A (RICOH CO. LTD.), 19 January 1990 (1990-01-19) *
See also references of WO0118123A1 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1375612A1 (de) * 2002-06-26 2004-01-02 Konica Corporation Tintenstrahltinte, Tintenstrahlaufzeichnungsverfahren und damit aufgezeichnetes bilderzeugendes Material
US6949135B2 (en) 2002-06-26 2005-09-27 Konica Corporation Ink-jet ink, ink-jet recording method and recorded imaging material using thereof

Also Published As

Publication number Publication date
CN1359411A (zh) 2002-07-17
EP1209204A4 (de) 2002-11-05
DE60008760D1 (de) 2004-04-08
WO2001018123A1 (fr) 2001-03-15
EP1209204B1 (de) 2004-03-03
CA2383143A1 (en) 2001-03-15
TW538098B (en) 2003-06-21
US6648952B1 (en) 2003-11-18
KR20020033103A (ko) 2002-05-04
KR100674095B1 (ko) 2007-01-26
DE60008760T2 (de) 2004-08-05
CN1314766C (zh) 2007-05-09

Similar Documents

Publication Publication Date Title
EP1209204B1 (de) Anthrapyridonverbindung, waessrige magenta tintenzusammensetzungen sowie tintenstrahlaufzeichnungsverfahren
CA2325484C (en) Novel anthrapyridone compounds, water-based magenta ink composition and method of ink-jet recording
EP1063268B1 (de) Wässrige magentatintezusammensetzung und verfahren zur tintenstrahlaufzeicnung
JP5085129B2 (ja) アゾ化合物、インク組成物及び着色体
KR20060003374A (ko) 신규 안트라피리돈 화합물, 수성 마젠타 잉크 조성물 및잉크젯 기록방법
JP3767879B2 (ja) 新規アントラピリドン化合物、水性マゼンタインク組成物及びインクジェット記録方法
JP4466987B2 (ja) アントラピリドン化合物、水性マゼンタインク組成物及びインクジェット記録方法
US20060005744A1 (en) Dye composition, ink composition, and method of ink-jet recording
KR20060123383A (ko) 트리스아조 화합물, 잉크 조성물 및 착색체
JP3957450B2 (ja) アントラピリドン化合物、水性マゼンタインク組成物及びインクジェット記録方法
JPWO2012002277A1 (ja) インク組成物、インクジェット記録方法及び着色体
US20080011191A1 (en) Novel Azo Compound or Salt, Ink Composition Comprising Such Azo Compound, and Colored Article
JP3957423B2 (ja) 水性マゼンタインク組成物及びインクジェット記録方法
JP4408492B2 (ja) アントラピリドン化合物、水性マゼンタインク組成物及びインクジェット記録方法
JP4360572B2 (ja) 新規アントラピリドン化合物、水性マゼンタインク組成物及びインクジェット記録方法
JP2023087956A (ja) アゾ化合物、およびこれを含有するインク組成物、ならびにこれを用いたインクジェット記録方法、インクジェットプリンタ、および着色体
JP5690747B2 (ja) インク組成物、インクジェット記録方法及び着色体
JPWO2012099059A1 (ja) 水溶性アゾ化合物又はその塩、インク組成物及び着色体
JP2019151784A (ja) アゾ化合物、インク組成物、記録方法及び着色体
EP1130064A1 (de) Farbstoffzusammensetzung, tintenzusammensetzung sowie tintenstrahlaufzeichnungsverfahren
US20120056931A1 (en) Magenta coloring matter, ink composition, and colored body
JP2016175997A (ja) トリスアゾ化合物、インク組成物、記録方法及び着色体
JP2014077077A (ja) アゾ化合物、インク組成物、記録方法及び着色体
JP2011074211A (ja) アゾ化合物、インク組成物、記録方法及び着色体
JP2013249321A (ja) アゾ化合物、インク組成物、記録方法及び着色体

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20020102

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

A4 Supplementary search report drawn up and despatched
AK Designated contracting states

Kind code of ref document: A4

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

A4 Supplementary search report drawn up and despatched

Effective date: 20021105

RIC1 Information provided on ipc code assigned before grant

Free format text: 7C 09B 5/14 A, 7C 09D 11/00 B, 7B 41M 5/00 B, 7B 41J 2/01 B, 7C 07D 221/18 B

17Q First examination report despatched

Effective date: 20030319

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE FR GB IT LI

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: CH

Ref legal event code: NV

Representative=s name: A. BRAUN, BRAUN, HERITIER, ESCHMANN AG PATENTANWAE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 60008760

Country of ref document: DE

Date of ref document: 20040408

Kind code of ref document: P

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20041206

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Owner name: NIPPON KAYAKU KABUSHIKI KAISHA

Free format text: NIPPON KAYAKU KABUSHIKI KAISHA#11-2, FUJIMI 1-CHOME, CHIYODA-KU#TOKYO 102-8172 (JP) -TRANSFER TO- NIPPON KAYAKU KABUSHIKI KAISHA#11-2, FUJIMI 1-CHOME, CHIYODA-KU#TOKYO 102-8172 (JP)

REG Reference to a national code

Ref country code: CH

Ref legal event code: PCAR

Free format text: NEW ADDRESS: HOLBEINSTRASSE 36-38, 4051 BASEL (CH)

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20150811

Year of fee payment: 16

Ref country code: GB

Payment date: 20150826

Year of fee payment: 16

Ref country code: DE

Payment date: 20150825

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20150629

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20150827

Year of fee payment: 16

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 60008760

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20160828

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160831

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160831

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20170428

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160828

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160831

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170301

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160828